Search Documents

By John W. Wagner, Robert K. Willardson

Single crystals of Pbl-xSnXTe have been grown from The melt under liquid B2O3 using the Czochralski technique. The PbTe-SnTe crystals were grown from near-stoichiometric melts and from melts with slight deviations from sloichiometry. Crystal growth rates ranging from 1 mm per hr to 1 cm per hr were employed, the latter being generally used. Several investigations were performed to characterize the single crystals grown In this study. The phase diagram of the PbTe-SnTe system was examined. X-ray analyses verified the single-crystal character of the crystals, and powder pattern lattice parameter determinations showed that Vegard's law was followed within the limits of the experimental error. The as-grown crystals were p-type with apparent carrier concentrations of -8 x 1018 to -8 x 1020 carriers per cu cm. Hall coefficients, resistivities, and carrier mobilities were determined as a function of composition. Dislocations were revealed by an electrolytic etch, and the crystals were found typically to contain 2 to 4 x 105 dislocations per sq cm. Microhardness measurements were performed; no maximum in the Vickers hardness us composition curve was seen. Mass spectrometry was used for impurity analyses, and the crystals were found to contain 1 to 2 x 1017 total p-type impurities per cubic centimeter. Distribution coefficients were calculated for the major impurities which were Na, Mg, Al, Si, Cl, and Zn. RECENTLY interest has been stimulated in the preparation and characterization of many alloys of the binary compound semiconductors. This interest is due primarily to the almost unlimited possibilities of adjusting the semiconducting characteristics of these materials by varying the alloy compositions. One alloy system which has been receiving extensive investigation is the PbTe-SnTe system, since these alloys show promise of being useful as emitters and detectors of electromagnetic radiation in the spectral range of 8 to 14 µ. This paper reports on the growth of PbTe-SnTe single crystals by the Czochralski technique and investigations of the general properties of these crystals. The phase diagram of the PbTe-SnTe system was investigated so that specific alloy compositions could be attained. I) CRYSTAL GROWTH The PbTe-SnTe single crystals were pulled from the melt using the Czochralski technique. Generally, the crystals were grown from near-stoichiometric melts, although special growth runs were made from both lead-rich and tellurium-rich melts. Growth of single crystals from up to 5 pct lead-rich melts presented no problems; however, melts with tellurium in excess of -1 pct caused volatilization problems which generally made crystal growth impossible. All melts were prepared from high-purity materials as follows: 1) lead— 6 N— Cominco (Cominco Products, Inc., Spokane, Wash.); 2) tin—5N—Cominco; and 3) tellurium— 5N+— American Smelting & Refining Co., Plainfield, N.J. No further purification of materials was undertaken in this study. The elements were reacted at -1000°C in a vacuum-sealed silica tube for a few hours, a gentle rocking action being used to ensure thorough reaction. The cast ingots were then transferred to a silica crucible for crystal growth. A schematic diagram of the growth apparatus is shown in Fig. 1. The Vycor tube is sealed at both ends by O-ring flanges so that a vacuum or a positive pressure may be maintained in the growth chamber. The pull rod and crucible may be rotated; all crystals produced in this study were grown with the crucible sta-

Jan 1, 1969

An account is given of experimental apparatus for generating a short duration high velocity water jet and the effect of its impingement on various rock samples under air or water cover. The penetration was found to be highly dependent upon the rock structure; in general material with closely interlocking grains was resistant.The damage sustained by a stationary sample held close to the jet did not vary greatly whether the sample was in air or confined under a water layer; but when the sample was translated under the jet there was a marked increase in the damage sustained.Some consideration was given to the possible practical application of a water jet for deep hole drilling and an estimate made of the power requirements and transmission losses for such a system.

Jan 1, 1969

By Jarrell C. Grout

The Bureau of Mines has developed a computer program for use in solving nonlinear regression problems. The program is written in a general form so that, regardless of the functional relationship, the unknown parameters may be evaluated by either the Gauss-Newton or the Newton-Raphson methods of iteration. Variances and covariances of the parameters, as derived from the law for the propagation of errors, are also determined.

Jan 1, 1969

By J. E. Korski

Quebec Cartier Mining Co. operates a low-grade iron ore deposit at Lac Jeannine, Que., which is located at the extreme southwestern end of the Quebec-Labrador Trough (Fig. 1). The facilities there include one of the world's largest concentrators, a hydroelectric plant of 60,000 hp, and the modern town of Gagnon. A 191-mile railway connects the mine to the seaport situated at Port Cartier on the St. Lawrence River. The harbor in Port Cartier can accommodate both lake and large ocean- going vessels and is also the site of a major grain terminal. The concentrator in Lac Jeannine is designed to produce some 8 million tpy (tons per year) of specular hematite concentrate, containing 66% Fe, from approximately 20 million tons of crude ore. An annual stripping program of 5 to 8 million cu yd of waste rock uncovers the required ore. Approximately 100,000 tons of ore and waste are removed daily on a year-round, 24-hr-per-day basis. The open pit covers an area with maximum dimensions of 8,000 x 2,600 ft (Fig. 2). Present mining plans call for an ultimate depth of approximately 1,000 ft below original ground level. The rocks in the pit area are typical of this portion of the Grenville geological province. They consist largely of marble, quartz rock, pegmatite, iron formation, and stratigraphically older gneisses. The iron-ore formation consists of medium to coarse-grained specular hematite in a quartz host rock. The formation occurs locally in a plunging, anticlinal form. The topography in the vicinity of the mine is rolling, with maximum variations in elevation of about 400 ft. The hills are thickly wooded with birch, black spruce, and some tamarack. Lakes and muskeg areas are plentiful. Precipitation and temperature records have been kept since 1959. The annual rainfall has ranged between a low of 23 in. and a high of 42 in.

Jan 1, 1969

By J. J. Jonas, J. L. Uvira

Equipment was constructed which permitted the hot compression of 99.8 pct Armco iron and 2.8 pct Si steel at constant true strain rates of 0.05 to 1 per sec over the temperature range 600" to 1000°C. A maximum true strain of 1.9 could be attained, followed by immediate quenching or by isothermal annealing. True stress-true strain curves were obtained, and the steady-state flout stress, a, strain rate, i, and temperature, T, were found to fit the following expression: The constants A, a, n', and AH were determined for the two ,materials. The activation energies obtained for Arrnco iron and silicon steel are 66 and 80 kcal per mole, respectively, and approximate those for seu- diffusion and for creep. This indicates that hot compression is a diffusion-controlled thermally activated process. THE hot compression of iron and steel is usually carried out in the austenite temperature range,1"7 as this is the one of greatest interest with respect to industrial hot working. However, a disadvantage of testing in the austenite range is that the hot-worked structure is destroyed by the phase transformations taking place during cooling. The present study was therefore carried out in the ferritic temperature range, and the hot-worked substructures were preserved by rapid quenching after deformation. The substructural results will be described in a separate paper, and the present communication is restricted to the strain rate/stress/temperature relationship observed during hot working. The results of hot-compression testing are usually given in the form of true stress/true strain curves, with a different curve for each temperature/strain rate ~ornbination.',~,~ Sometimes simple algebraic equations are fitted to the curves, so that certain extrapolations or interpolations can be performed.1'2'5 These equations are, however, devoid of mechanistic interpretations. The present study was undertaken to show that hot compression can be described by an equation of the type used in creep studies. That is, it will be shown that the temperature dependence of the strain rate in hot working is well-represented by an Arrhenius term, with an activation energy similar to that for creep. Also it will be seen that the stress dependence of the strain rate is similar to that for creep EXPERIMENTAL METHOD AND MATERIALS The investigation was carried out with the following three ferrous materials: 1) Armco iron; 2) Armco iron with 0.26 pct Mn; 3) 2.8 pct Si steel. The first two materials were utilized for investigations performed in the temperature range 600" to 800°C; the last one was used for tests at temperatures from 600" to 1000°C. The materials were of commercial purity,* as shown in Table I. Cylinders of five different sizes were prepared by strain annealing. The resulting mean grain diameter was 3 mm in the 1-in. Armco iron and 2 mm in the other sizes and grades. Different ratios of diameter/height were used to enable the determination of the coefficient of friction. The specimen faces were provided with concentric grooves, which acted as lubricant holders during compression, as recommended by English and ~ackofen' and others.2'9 Powdered glass lubricants were applied to the samples before hot compression to decrease friction and barreling, following the practice of previous investigator~.~~~~~~~~ Different mixtures of glass powder were used for each temperature, after the determination of suitable compositions by experiment.'' Equipment for Hot Compression. Hot-compression tests were carried out on an adapted 150-ton vertical hydraulic extrusion press and also on a modified high-temperature creep machine. The modified extrusion press was used for temperatures up to 800°C. The following items were added to the press: a) a high-temperature furnace with built-in upper and lower platens; and b) a transmission assembly, which permitted the attainment of logarithmically decreasing crosshead speeds. These accessories are described in detail in Ref. 11.

Jan 1, 1969

By W. A. Haley

This paper discusses how a large wheel loader should be equipped, with particular attention paid to tires and tread life, and describes the several steps that can be taken to provide favorable working conditions and reduce over-all costs. A comparison is then made of wheel loader production and costs vs those of power shovels, and the present and possible future applications of the wheel loader are outlined.

Jan 1, 1969

By J. Brett, L. Seigle, L. Castleman, T. Montelbano

Impurity-induced low-temperature recrystallization of cold-worked tungsten was inuestigated with emphasis on the influence of nickel on the reaction. Palladium, nickel, aluminum, manganese, platinum, and iron greatly lower the recrystallization temperature of doped tungsten, which zs normally very high, but the recrystallization temperature of electron-be am zone-refined tungsten wzre is slightly raised by conlacl with nickel. Recrystallization can be induced at low temperature by the presence of solid nickel on the surface of doped tungsten wire, but apparently not by exposure to nickel vapors alone. Approximately 200 ppm of Ni dijjused into 10-mil wires at 1200 from a deposit of nickel on the surface produced total recrystallization, whereas more than 600 ppm of Ni could be absorbed frotn a vapor source without altering the fibrous structure of cold-worked tungsten. Once initiated, nickel-induced recrystallization required a continued source of' nickel for propagation of the recrystallization front. The solubility of nickel in fibrous 10-mil W wire was approximalely 500 ppm at 1150' C, and the activation energy for penetration of the recrystallization front was 52 kcal per mole. In many applications the usefulness of tungsten depends on critical control of its structure. Cold-worked tungsten with the fibrous structure developed by suitable thermo-mechanical treatment has a low, but technologically significant, ductility. It has long been known1 that traces of nickel, and perhaps other metals, are profoundly deleterious in doped tungsten, because they induce recrystallization at low temperature, which produces a brittle, equiaxed grain structure. This effect appears to be an exception to the general observation that recrystallization is impeded and the recrystallization temperature raised by the presence of impurities.2"9 Previous studies7-'' of the annealing and recrystallization of tungsten wire have divided the phenomenon into prior recovery stages, primary recrystallization and secondary recrystallization. The present investigation is concerned principally with primary recrystallization which is defined here as the replacement of the fibrous structure of deformed tungsten by equiaxed grains. The objective of this study was to explore the nickel-induced recrystallization reaction in tungsten and attempt to elucidate its mechanism. As well, an effort to define which other elements give rise to low-temperature-induced recrystallization was carried out. EXPERIMENTAL PROCEDURE The procedure adopted for these experiments was essentially to bring nickel and other elements into diffusive contact with cold-worked tungsten wires. The process of recrystallization was followed as a function of time and temperature by light and electron microscopic observations. First the influence of nickel on the recrystallization temperature of arc-melted, zone-refined, and variously doped tungsten wire was determined by electroplating a deposit of nickel on the surface of the wire and annealing at a variety of temperatures for 3 hr. The chemical analyses of the tungsten wires used in this investigation are given in Table I. The surface of the tungsten wire was etched with Murakami's slution' and approximately 0.005 in, of Ni was deposited from a Watts-type low pH bath14 for the conditions of these experiments. Variations in plating thickness from about 0.001 to 0.005 in. had no discernible influence on the resulting structures. The wires were then annealed in an atmosphere of dry hydrogen to establish the recrystallization temperature. Concurrently, un-plated specimens were annealed to establish the recrystallization characteristics of nickel-free wire. The criterion of recrystallization was that the fibrous structure be completely replaced by equiaxed grains after a 3-hr treatment of temperature. This provided more reproducible results than use of the first recrystallized grain or a fixed proportion of re-crystallized structure as the critical observation. The structures encountered in longitudinal and transverse sections were examined by both light and electron microscopy at magnifications up to X32,000 using parlo-dion-carbon replicas shadowed with platinum for the latter method. Second, the influence of a variety of metals on the recrystallization temperature of 0.010 in. D alumina-silica doped tungsten wire, AW136-64, was determined. The elements were applied by electroplating whenever possible. Alternatively, they were vapor-plated on the tungsten wire and a greater thickness built up by coating with a dispersion of metal powder in nitrocellulose lacquer. Elements not amenable to either of these procedures were merely slurry coated on the tungsten. The recrystallization temperature was determined as above. Third, the nickel-induced recrystallization process in doped wire was studied more closely by electroplating 8 mils of Ni on 65-mil alumina-silica doped tungsten wire, AW153-NS10, and exposing the wire to temperatures of llOO°, 1200°, or 1300°C for various times in a hydrogen atmosphere. A circular recrystallization front, 'Onsisting of equiaxed grains, developed at the periphery Of the coated tungsten wire, and the advance of this front into the fibrous interior was studied. These experiments employed relatively coarse 0.065 in. D wire because the 0.010 in. D wire recrystallized too quickly to permit observation of the pene-

Jan 1, 1969

This method determines tellurium at concentrations down to 0·01 p.p.m., with geochemical accuracy. Tellurium is volatilized from the rock at 800°C in the presence of sulphur from decomposing pyrite, condensed, dissolved, and finally determined by atomic absorption in a long tube burner. The distribution of Te is shown near some gold lodes at Kalgoorlie. Lastly, a method of synthesizing Te-free pyrite from sulphur and ferrous sulphate is described.

Jan 1, 1969

By H. T. Kennedy, S. M. Avasthi

An equation developed for gaseous hydrocarbon mixtures predicts molal volumes with an average absolute deviation of 0.73 percent when applied to 264 natural gas and condensate systems including 2,043 PVT points. Another equation developed for liquid hydrocarbon mixtures predicts molal volumes with an average absolute deviation of 1.12 percent when applied to 346 crude oil systems including 1,759 PVT points. Both equations require composition of the mixture to be expressed as mole fraction of methane through heptanes-plus, hydrogen sulfide, nitrogen and carbon dioxide, together with the characteristics of the heptanes-plus fraction in addition to the temperature and pressure. The equations cover wide ranges of the variables involved, and their accuracy is considerably better than that of other available methods. The equations were differentiated to allow calculation of the coefficients of isothermal compressibility and isobaric thermal expansion. (In this paper the coefficient of isothermal com-pressibility and the coefficient of isobaric thermal expansion will be expressed as compressibility and thermal expansion coefficient, respectively.) Equations to calculate these quantities are presented. INTRODUCTION Calculations of reservoir performance for petroleum reservoirs require accurate knowledge of the volumetric behavior of hydrocarbon mixtures, both liquid and gaseous. Compressibilities are required in transient fluid flow problems, and thermal expansion coefficients are important in thermal methods of production. An accurate laboratory investigation of the PVT behavior of each reservoir fluid encountered would be costly and time consuming. For this reason various correlations for predicting fluid properties have been developed and recorded in recent literature. Correlations have been presented in the form of graphs, tables and equations. Since an increasing number of studies are being conducted with the aid of electronic computers, recent efforts have been directed toward development of correla-tions suitable for computer programming. Application of computers permits the use of more complex correlations which otherwise are not feasible. Moreover, methods for predicting reservoir performance, particularly those based on the compositional material balance, depend upon the capability of accurately expressing the molal volumes and other fluid properties as functions of pressure, temperature and composition. The coefficient of isothermal compressibility c is defined by

Jan 1, 1969

Jan 1, 1969

By John T. Dickman, Ralph E. O’Dette

Chemical Abstracts Service (CAS) is in the process of evolving a computer-based information system which will process all of the material selected for abstracting in the area of chemistry and chemical engineering and its related fields such as the earth sciences and technologies. This system is already operational to some extent and is expected to be fully utilized by 1971. The objective of CAS is to make chemical and related information more readily available, more usable and more used. Chemical Abstracts handle some 5000 abstracts weekly from 13, 000 journals and patents from 25 nations. These cover all of the 80 CA subject sections which relate to chemistry and also extend into areas of interest to geologists, mineralogists, and mining engineers. In this way, CAS fulfills its objective of complete coverage of its major fields, informative abstracting, and indexing to maximum specificity. The concept of a computer-based information system is that of a single machine-language data base into which the results of intellectual analysis of the literature are entered and from which computer programs produce a variety of publications and services applicable to the needs of a wide range of users.

Jan 1, 1969

By Neil H. Bostick

This research, sponsored at Stanford Research Institute by the Grand Junction Operations Office of the U.S, Atomic Energy Commission, was an outgrowth of the concern that presently-known ore reserves may be inadequate to meet the projected demands of nuclear power reactors. The original program at SRI was to design a comprehensive geological information system and use it to store and analyze the very great quantity of data needed to estimate uranium ore reserves. Study of the problem showed that it could be solved only by use of modern electronic data processing techniques, so such a comprehensive system was designed and tested. The system test was satisfactory, but input lead time and total expense were shown to be too great for the system to be practicable for the AEC under present circumstances. Thus, based on results of the earlier research, a specialized and simplified procedure for predicting approximate uranium ore reserves was devised. The prediction is based on general geology of specific area cells of the earth, in order to provide complete volume coverage; the strata in these ores are evaluated for uranium ore favorability on the basis of a few selected criteria in order to allow rapid data input. Since the bulk of U.S. reserves are in clastic host rocks only such strata are considered in this work. This paper describes the structure and some details of the resource system and how it was tested in rn area of the western United States.

Jan 1, 1969

By E. L. Burwell

Preliminary results of an in situ oil shale retorting experiment conducted by the Bureau of Mines in a shallow bed of Green River oil shale at Rock Springs, Sweetwater County, Wyo., are described. Eleven wells were drilled into a 20-ft-thick section of the shale lying between 68 and 88 It deep, and attempts were made to connect the wells through the shale with a fracture system created by application of high-voltage electricity (electro-linking), hydraulic fracturing, and explosive fracturing. Ignition of the shale through the central well was easily achieved with a propane burner, and shale oil began to collect in three wells within 3 hours. Propane injection was discontinued after 7 days, and combustion continues, although attempts to control the direction of the combustion front have been unsuccessful. Production rates as high as 4 ½ barrels of nil per day have been recorded, but too little is known about underground conditions to permit an estimate of recovery efficiency at this time.

Jan 1, 1969

By Phillip E. Deering, Robert M. Cox

A model pillar study was conducted in which the engineering principles of dimensional analysis were applied to the problem of coal mine pillar design. The paper reviews the theory of similitude as applied to the model pillar study conducted in the investigation. An example solution of a design problem is included to indicate how the results of the study may be used as a first approximation in the design of coal mine pillars. The design of mine pillars for adequate support with minimum loss of valuable raw materials has always presented a problem to the mining engineer. Most often, for lack of a better method, past practice has influenced the design of new mine pillars. This process has always left doubt as to the safety factor of the pillars. The work presented in this paper is an initial attempt toward adapting the engineering principles of dimensional analysis to the problem of pillar design in underground mines. The use of the dimensional analysis technique is advantageous because all the variables associated with the problem are considered, and by systematic analysis the relative influence of each variable is determined. The model material utilized in this study was taken from the Helena seam of the Cahaba coal field located in central Alabama. The research study was sponsored by The Southern Electric Generating Co. as part of an over-all rock mechanics investigation of the Helena seam area. THEORY OF SIMILITUDE Model analysis is used extensively in engineering today, particularly in the solution of design problems that defy the classical methods of analysis. Such problems arise when materials with a nonlinear stress-strain relationship are involved, when geo- metric boundaries are difficult to define in simple form, when strains become large, or when partial failure occurs. All of these difficulties usually exist in pillar design problems. Those principles which underlie proper design and construction of models, and the interpretation of test results, comprise the theory of similitude. That is, the theory of similitude includes a consideration of the conditions under which the behavior of two separate entities or systems will be similar, and the techniques of accurately predicting behavior of one from observation of the other. The theory of similitude may be developed by dimensional analysis. Dimensional analysis, as a powerful analytical tool, is developed from a consideration of the dimensions in which each of the important quantities involved in a phenomenon is expressed. It is based on two axioms: 1) Absolute numerical equality of quantities may exist only when the quantities are similar qualitatively. 2) The ratio of the magnitudes of two like quantities are dependent on the units used in their measurement, provided that the same units are used for evaluating each. Dimensional analysis, developed from these two axioms, differs from other types of analysis in that it is based solely on the relationships that must exist among the pertinent variables because of their dimensions, rather than on the relationship of natural laws. In itself, dimensional analysis ~rovides qualitative, rather than quantitative relationships, but when it is combined with experimental procedures, it may be made to supply quantitative results and accurate prediction equations. APPLICATION OF THEORY The design of an adequate mine pillar requires the determination of a design equation and the selection of a dimensional system with which to work. Since force plays an important part in the design of mine support, the FLT (force, length, time) system has been used. The factors involved in the dimensional analysis of mine pillars and their dimensions are: A = cross-sectional area L Cp = design strength FL- E, = tangent modulus of elasticity FL

Jan 1, 1969

Very little has been written about the discovery and early history of prospecting of ironstone deposits in the Iron Knob-Middleback Range area of South Australia, the main source of supply of ironstone (hematite) for the Australian steel industry, and scanty though the record is, much of it is wrong or misleading.With the help of several people, to whom acknowledgement is made at the end of the paper, the writer has unravelled some of the story, but not the whole story. It is hoped that publication of this paper will stimulate interest in others, who may be able to supplement this account from family records, from the files of newspapers, or from archives.

Jan 1, 1969

By Goodman, Richard E.

A complete rational analysis for design of excavation slopes and loaded rock masses is a desirable but perhaps unattainable goal. Irregular external and internal boundary conditions, poor understanding of failure criteria for large masses of rock, capricious material properties, and the importance of indeterminate forces and inaccessible and virtually un- sampleable rock defects emphasize the importance of experience in this aspect of rock engineering. The experience must be correlated with geological factors. In certain regions the accumulation of such experience through the observation of existing rock slopes in various formations constitutes an important aspect of studies for design of rock excavations.

Jan 1, 1969

By J. Campbell

The hydrostatic tensions in pure metals and long freezing range alloys are evaluated theoretically considering the viscous flow of residual liquid and the general plastic collapse of the casting. The former mechanism operates until the radii of the remaining liquid channels are of the order of 10-3 cm radius, after which the second process limits the attainable negative pressures which range from —1500 to -4200 atm for nickel, aluminum, copper, and iron. In previous reports1'2 the maximum possible hydrostatic tensions developed during solidification have been evaluated employing spherical symmetry. This inevitably involves the concept of totally confined liquid regions, the reality of which has recently been brought into serious doubt3 following observations of the freezing of various transparent materials. Regions of interdendritic liquid which are apparently about to be isolated by the growth of dendrite arms are observed not to be cut off because the advance of the dendrite tips is arrested until the region has completely solidified. Although this may be the result of the very low melting point liquid available at this late stage in freezing, or the result of a higher rate of heat transfer to the dendrite tips because of the acceleration in liquid flow rate near the completion of solidification, this point need not concern us. In this paper an attempt is made to approximate more closely to real conditions; thus the assumption of confined liquid regions is abandoned and cylindrical symmetry adopted. It has also been necessary, therefore, to consider the viscous flow of residual liquid through the remaining channels in the pasty zone. Furthermore, the rather special conditions of spherically symmetric solidification led to extremely high solidification rates and hence unusually high tensile stresses as solidification neared completion; the cylindrical Symmetry appears to yield solidification rates and stresses which are more typical of real castings. The rate of solidification is first considered since this critically affects both the flow of the liquid and the creep of the solid.

Jan 1, 1969

By Robert C. Linares

Cubic zinc sulfide has been grown from molten salt solutions substantially below the hexagonal-cubic phase transition of 1020°C. Crystals free of birefringence have been grown from molten lead chloride at temperatures from 500° to 800°C. Factors affecting the optical transmission and the birefringence are discussed. CUBIC zinc sulfide is of interest for electrooptic devices and as an optical coating material. However, it cannot readily be produced as large crystals which are free of birefringence. The birefringence arises from the fact that the cubic ZnS is usually grown as the high-temperature hexagonal phase and is transformed to the lower cubic phase by annealing.' This results in stacking faults, stress, and birefringence. A requirement for the growth of cubic ZnS is that it be grown below the phase transition of 1020°C.2 Crystals of cubic ZnS have been grown below 1020°C by the hydrothermal,3 flux,4 and vapor transport5 techniques. However, these all appear to have limitations in size or quality of material produced. It was felt that a new flux method might have a good chance of overcoming some of the previous problems. Mita6 reported the growth of hexagonal ZnS from molten NaCl and wilke7 reported the growth of iron sulfides from molten lead chloride solution, indicating that molten chlorides make good solvents for sulfides. An investigation of a number of possible molten chlorides as solvents showed that molten PbCl2 has an appreciable solubility for zinc sulfide and that crystals can be grown at temperatures from 500° to 800°C. EXPERIMENTAL Crystal growth was performed in open or sealed Vycor or fused silica tubes, in an argon atmosphere or vacuum. There were no deleterious effects due to using vacuum; however, a sealed essentially isothermal system must be used to prevent vapor transport mechanisms from dominating. This will be discussed later in detail. Noble metal containers were not usable as they were severely attacked by these melts. The materials used were: reagent-grade PbC12, reagent-grade ZnS, optical-coating-grade ZnS, and Irtran 2 (ZnS). Crystal growth was accomplished by both slow cooling techniques and gradient growth techniques. In the slow cooling techniques, 15 g of ZnS and 100 g of PbCl2 were used. The components were placed in the silica tube, heated at 800°C for 2 hr, and then slowly cooled (l° to 10° C per hr) to 500°C. The furnace was constructed so that the tube could be inverted, thus allowing the liquid to drain off the crystals at the end of the run. The gradient runs were made by placing the above mixtures in a silica tube at 550° to 600°c, Fig. 1. A temperature gradient was maintained such that the floating mass of undissolved sulfide was 10° to 50°C warmer than the bottom of the tube. Growth occurred on spontaneously nucleated sites at the cooler bottom. RESULTS When using high cooling rates (5° to 10°C per hr), crystals form in thin sheets perpendicular to the {111} face. Crystals 5 by 5 by 1.2 mm, Fig. 2, have been ob-

Jan 1, 1969

The mineralogy and textures of a portion oC ore from the 25 level northern orebody, North mine, Broken Hill are described. This ore, in places, contains up to 70 per cent cubanite (CuFe2S3 ) which has crystallized directly with other sulphides and associated gangue minerals.Several breakdown reactions involving the cubanite are also considered.

Jan 1, 1969

Jan 1, 1969